High-temperature measurements of the rates of the reactions CH2O + Ar → Products and CH2O + O2 → Products

The two-channel thermal decomposition of formaldehyde [CH₂O], (1a) CH₂O + Ar → HCO + H + Ar, and (1b) CH₂O + Ar → H₂ + CO + Ar, was studied in shock tube experiments in the 2258-2687 K temperature range, at an average total pressure of 1.6 atm. OH radicals, generated on shock heating trioxane-O₂-Ar mixtures, were monitored behind the reflected shock front using narrow-linewidth laser absorption. 1,3,5 trioxane [C₃H₆O₃] was used as the CH₂O precursor in the current experiments. H-atoms formed upon CH₂O and HCO decomposition rapidly react with O₂ to produce OH via H + O₂ → O + OH. The recorded OH time-histories show dominant sensitivity to the formaldehyde decomposition pathways. The second-order reaction rate coefficients were inferred by matching measured and modeled OH profiles behind the reflected shock. Two-parameter fits for k_1a and k_1b, applicable in this temperature range, are:

     

Two-photon standing-wave fluorescence correlation spectroscopy

A fluorescence correlation spectroscopy experiment that combines two-photon excitation and a standing-wave interference pattern is presented. The experimental correlation function can be analyzed using a simple expression involving (1) an exponential decay with time constant tau(f), which reflects diffusion across the interference fringes, and (2) a longer-lived decay with time constant tau(omega), which reflects diffusion in and out of the focal spot. The diffusion of Rhodamine 110 in water and ethylene glycol is measured using this method. The ability to simultaneously measure diffusion on two different time and lengthscales makes this experiment especially useful in environments where anomalous diffusion is suspected.     

Lactose as a “Trojan Horse” for Quantum Dot Cell Transport

A series of glycan‐coated quantum dots were prepared to probe the effect of glycan presentation in intracellular localization in HeLa and SV40 epithelial cells. We show that glycan density mostly impacts on cell toxicity, whereas glycan type affects the cell uptake and intracellular localization. Moreover, we show that lactose can act as a “Trojan horse” on bi‐functionalized QDs to help intracellular delivery of other non‐internalizable glycan moieties and largely avoid the endosomal/lysosomal degradative pathway.     

Ring-Closing Metathesis Strategies to P -heterocycles

A general approach to the synthesis of P -heterocycles using the ring-closing metathesis reaction is described. We have developed a new method utilizing phosphorus nuclei as suitable temporary tethers for the coupling of non-racemic allylic amines. This approach allows for the generation of symmetric and unsymmetric 1,4-diamines. Subsequent coupling of these 1,4-diamines with various nuclei produces an array of 7-membered heterocycles.     

Diterpenoids

The review covers the isolation and chemistry of diterpenoids including labdanes, clerodanes, pimaranes, abietanes, kauranes, gibberellins, cembranolides, taxanes and marine diterpenoids. The literature from January to December 2000 is reviewed and 157 references are cited.     

Conformationally constrained alpha-boc-aminophosphonates via transition metal-catalyzed/curtius rearrangement strategies

A transition metal-catalyzed/Curtius rearrangement sequence toward the development of conformationally constrained alpha-Boc-aminophosphonates 2-6 is described. An approach using the versatile tert-butylphosphonoacetate moieties 1a and 1b to derive an array of mono- and bicyclic alpha-Boc-aminophosphonate systems is presented. Conformational constraint is incorporated using either the ring-closing metathesis reaction catalyzed by the first generation Grubbs catalyst or intramolecular cyclopropanation mediated by Rh2(OAc)4. Using the tert-butyl ester functionality in 1a or 1b as a potential amino group, the Curtius rearrangement provides an efficient route toward the target alpha-Boc-aminophosphonates.     

Out-of-equilibrium Kondo effect in a mesoscopic device

We study the nonequilibrium regime of the Kondo effect in a quantum dot laterally coupled to a narrow wire. We observe a split Kondo resonance when a finite bias voltage is imposed across the wire. The splitting is attributed to the creation of a double-step Fermi distribution function in the wire. Kondo correlations are strongly suppressed when the voltage across the wire exceeds the Kondo temperature. A perpendicular magnetic field enables us to selectively control the coupling between the dot and the two Fermi seas in the wire. Already at fields of order 0.1 T only the Kondo resonance associated with the strongly coupled reservoir survives.